EP0212940A2 - Verfahren zur Herstellung einer Graphiteinlagerungsverbindung - Google Patents

Verfahren zur Herstellung einer Graphiteinlagerungsverbindung Download PDF

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Publication number
EP0212940A2
EP0212940A2 EP86306249A EP86306249A EP0212940A2 EP 0212940 A2 EP0212940 A2 EP 0212940A2 EP 86306249 A EP86306249 A EP 86306249A EP 86306249 A EP86306249 A EP 86306249A EP 0212940 A2 EP0212940 A2 EP 0212940A2
Authority
EP
European Patent Office
Prior art keywords
chloride
reaction
graphite
metal chloride
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86306249A
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English (en)
French (fr)
Other versions
EP0212940B1 (de
EP0212940A3 (en
Inventor
Tsutomu Nippon Steel Corp. Sugiura
Maki Nippon Steel Corp. Sato
Kenichi Nippon Steel Corp. Fujimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Corp
Nippon Steel Chemical Co Ltd
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Filing date
Publication date
Application filed by Nippon Steel Corp, Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Corp
Publication of EP0212940A2 publication Critical patent/EP0212940A2/de
Publication of EP0212940A3 publication Critical patent/EP0212940A3/en
Application granted granted Critical
Publication of EP0212940B1 publication Critical patent/EP0212940B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation

Definitions

  • This invention relates to a method for the production of a graphite intercalation compound. More particularly, this invention relates to a method for the production of a graphite intercalation compound which, by effecting the reaction for the production in the presence of a second metal chloride besides the metal chloride destined to form the intercalant aimed at, notably shortens the time required for the synthesis of the graphite intercalation compound and permits the synthesis to be carried out effectively without using chlorine.
  • the graphite intercalation compounds have been found to combine the chemical stability inherent in graphite and other properties with high degrees of electroconductivity proper to metals. The knowledge has encouraged numerous researches. These researches have unveiled the fact that graphite intercalation compounds have their nature governed by the kinds of intercalants inserted therein.
  • the graphite intercalation compound which has an alkali metal such as, for example, potassium as an intercalant
  • the graphite intercalation compound lacks stability in the air and yields to decomposition, though it enjoys improved electroconductivity (Y. Iye et al., Phys. Rev. B, 25, 4583, 1982).
  • the graphite intercalation compounds using metal chlorides as their intercalants possess degrees of electroconductivity that fall short of that of copper metal but compare favorably with those of almost all metals and, what is more, enjoy stability in the air.
  • the graphite intercalation compound is stable not only in the air but also under water.
  • the reaction for the intercalation of cupric chloride into graphite proceeds so slowly that some tens of days are required for completion of the reaction (Takahashi et al., Glossary of Lectures for the llth Annual Meeting of The Carbon Society of Japan, page 42, 1984). Owing to the slowness of the reaction, quantity use of the compound has proved virtually impracticable.
  • the inventors have continued a diligent study for the purpose of solving the problems and notably increasing the velocity of the reaction. They have consequently found that the velocity of the reaction can be heightened by allowing a second metal chloride of a low boiling point to be present in a minute amount in the reaction system and that the presence of the minute amount of the second metal chloride of a low boiling point enables the reaction for which the presence of chlorine gas has been found an indispensable requirement to proceed to completion in the absence of chlorine gas.
  • the present invention has been perfected as the result.
  • a metal chloride such as, for example, ferric chloride, cupric chloride, nickel chloride, aluminum chloride, or cobalt chloride
  • a specific metal chloride such as, for example, nickel chloride
  • this invention aims to provide a method which is characterized by allowing the reaction for the production to proceed in the presence, besides the metal chloride intended for the intercalation, of a second chloride having a realtively low boiling point and in the absence of chlorine gas.
  • a metal chloride such as, for example, ferric chloride, cupric chloride, aluminum chloride, nickel chloride, cobalt chloride, manganese chloride, or chromium chloride
  • a metal chloride such as, for example, ferric chloride, cupric chloride, aluminum chloride, nickel chloride, cobalt chloride, manganese chloride, or chromium chloride
  • a second metal chloride of a relatively low boiling point such as, for example, ferric chloride (boiling point, 317°C), aluminum chloride (sublimation point 183°C), cupric chloride, or cobalt chloride and, in the production of a graphite intercalation compound using a specific metal chloride such as, for example, nickel chloride previously held capable of inducing successful synthesis of the compound only under an atmosphere of chlorine, obviates necessity for use of chlorine by the use of a minute amount of the second metal chloride.
  • a specific metal chloride such as, for example, nickel chloride previously held
  • Preferred metal chlorides which have relatively low boiling points and are usable as said second metal chloride comprise those which have boiling points or sublimation points of not more than 320°C as described above, and those which have higher vapor pressures at the reaction temperature than the vapor pressures that the intercalants have.
  • the production of a graphite intercalation compound in accordance with this invention may be attained by charging a reaction vessel with graphite, a metal chloride intended as an intercalant, and a minute amount of a second metal chloride as an additive, vacuumizing the reaction vessel, and sealing it tightly, and allowing the contens thereof to react.
  • Any of the various kinds of graphite known to produce graphite intercalation compounds can be used as the graphite for the sake of the reaction.
  • Powdery natural graphite, sheetlike natural graphite, sheetlike swelled graphite, graphite fibers, and man-made graphite are examples.
  • the amount of the second metal chloride to be added may be in the range of 0.1 to 2.0 % by weight, preferably 0.3 to 2.0% by weight, based on the metal chloride intended as an intercalant. If the second metal chloride is added in an amount exceeding the upper limit of the aforementioned range, there is the possibility that the pressure inside the reaction vessel will rise so much as to jeopardize the safety of the reaction and the second metal chloride will mingle in a large amount in the product and render the control of characteristics such as, for example, thermal stability and electroconductivity difficult. If the amount of the second metal chloride to be added is less than the lower limit of the aforementioned range, the velocity of the reaction is not heightened so much as expected.
  • the reaction vessel charged with the raw materials described above may be heated to a temperature in the range of 200°C to 700°C , though variable with the particular kind of metal chloride intended for intercalation, to induce reaction of the raw materials and give rise to the graphite intercalation compound aimed at.
  • the addition of a minute amount of a metal chloride other than the metal chloride intended for intercalation between graphite layers is recognized to bring about a notable increase in the velocity of the reaction.
  • the exact mechanism responsible for the acceleration of the reaction remains yet to be elucidated.
  • the accelerated reaction velocity may be logically explained by a postulate that when the added metal chloride of a relatively low boiling point such as, for example, ferric chloride or aluminum chloride is inserted into the graphite layers or when the chlorine generated in consequence of thermodynamic equilibrium is incorporated between the graphite layers in the initial stage of reaction, it confers electric charge upon the graphite layers and consequently activates the reaction for the intercalation of the metal chloride between the layers; and that the added metal chloride partly forms a metal chloride complex and consequently increases the apparent gaseous partial pressure of the metal chloride intended for intercalation between graphite layers.
  • a relatively low boiling point such as, for example, ferric chloride or aluminum chloride
  • This invention in the production of a graphite inter- calatin compound using a metal chloride as an intercalant, provides a method of production which permits a notable reduction in the reaction time heretofore protracted so much as to raise a problem. Further, in the production of a graphite intercalation compound using as an intercalant thereof a specific metal chloride capable of inducing the synthesis of the compound only under an atmosphere of chlorine, this invention obviates the necessity for use of chlorine gas owing to the addition of a second metal chloride. Thus, this invention decreases the heating time required during the course of the reaction and brings about an effect of saving energy consumption. Since it permits synthesis of the graphite intercalation compound without use of chlorine, a highly corrosive gas, it contributes to improving the work environment.
  • graphite intercalation compounds may be of light weight, good electroconductivity proper to metals, and highly stable in air; and have many uses such as for a light leading wire, EMI shield materials, electroconductive paint, packings, compound, etc..

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP86306249A 1985-08-17 1986-08-13 Verfahren zur Herstellung einer Graphiteinlagerungsverbindung Expired - Lifetime EP0212940B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60180046A JPS6241706A (ja) 1985-08-17 1985-08-17 黒鉛層間化合物の製造方法
JP180046/85 1985-08-17

Publications (3)

Publication Number Publication Date
EP0212940A2 true EP0212940A2 (de) 1987-03-04
EP0212940A3 EP0212940A3 (en) 1988-03-16
EP0212940B1 EP0212940B1 (de) 1991-03-27

Family

ID=16076537

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86306249A Expired - Lifetime EP0212940B1 (de) 1985-08-17 1986-08-13 Verfahren zur Herstellung einer Graphiteinlagerungsverbindung

Country Status (4)

Country Link
US (1) US4729884A (de)
EP (1) EP0212940B1 (de)
JP (1) JPS6241706A (de)
DE (1) DE3678360D1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0311298A2 (de) * 1987-10-06 1989-04-12 Cabotex Co. Ltd. Verfahren zur Bereitung einer Einlagerungsverbindung Bereitung einer Einlagerungsverbindung
EP0578887A1 (de) * 1992-07-17 1994-01-19 Inland Steel Company Verfahren zur Herstellung von Einlagerungsverbindungen
DE102021207914A1 (de) 2020-12-15 2022-06-15 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zum Herstellen eines elektrisch leitfähigen Leiterstrangs mit zumindest einem Kohlenstoffleiter
WO2022128495A1 (de) 2020-12-15 2022-06-23 Robert Bosch Gmbh Verfahren zum herstellen eines elektrisch leitfähigen leiterstrangs mit zumindest einem kohlenstoffleiter

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138315A (ja) * 1985-12-10 1987-06-22 Fuji Carbon Seizosho:Kk 金属塩化物と黒鉛とからなる層間化合物の製造方法
JPS62265112A (ja) * 1986-05-13 1987-11-18 Nippon Steel Corp 黒鉛層間化合物の製造方法
US4837377A (en) * 1987-12-28 1989-06-06 Trustees Of Boston University Rubbery, electrically non-conductive, and intrinsically magnetic graphite intercalation compounds and methods for their making
US4987175A (en) * 1988-11-21 1991-01-22 Battelle Memorial Institute Enhancement of the mechanical properties by graphite flake addition
US5065948A (en) * 1988-11-21 1991-11-19 Battelle Memorial Institute Apparatus for producing thin flakes
US5019446A (en) * 1988-11-21 1991-05-28 Battelle Memorial Institute Enhancement of mechanical properties of polymers by thin flake addition and apparatus for producing such thin flakes
JPH02153812A (ja) * 1988-12-06 1990-06-13 Fuji Carbon Seizosho:Kk 二種類以上の金属ハロゲン化物を同時に挿入させた黒鉛層間化合物、及び製造方法
JPH04171605A (ja) * 1990-11-02 1992-06-18 Alps Electric Co Ltd 導電性ペースト
JPH04170310A (ja) * 1990-11-02 1992-06-18 Alps Electric Co Ltd 黒鉛層間化合物およびその製造方法
JP3434928B2 (ja) * 1995-04-03 2003-08-11 科学技術振興事業団 グラファイト層間化合物およびその製造方法
WO2007130869A2 (en) * 2006-05-01 2007-11-15 Yazaki Corporation Organized carbon and non-carbon assembly and methods of making
BRPI0703826A2 (pt) * 2007-08-28 2009-04-28 Nac De Grafite Ltda bateria alcalina
CN105655002B (zh) * 2014-11-27 2017-06-23 松下知识产权经营株式会社 导电材料

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2196293B1 (de) * 1972-08-18 1975-03-07 Armand Michel
US4565649A (en) * 1974-08-23 1986-01-21 Intercal Company Graphite intercalation compounds
GB1522808A (en) * 1974-08-23 1978-08-31 Vogel F L Graphite intercalation compounds
US4477374A (en) * 1981-10-03 1984-10-16 Central Glass Co., Ltd. Ternary intercalation compound of a graphite with a metal fluoride and fluorine, a process for producing the same, and an electrically conductive material comprising the ternary intercalation compound
US4604276A (en) * 1983-09-19 1986-08-05 Gte Laboratories Incorporated Intercalation of small graphite flakes with a metal halide
US4608192A (en) * 1984-01-16 1986-08-26 Gte Laboratories Incorporated Graphite intercalates containing metal-charge transfer salts
US4560409A (en) * 1984-08-29 1985-12-24 Superior Graphite Metal bearing graphitic carbons

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 92, no. 14, 7th April 1980, page 697, abstract no. 121021r, Columbus, Ohio, US; A.V. NEFED'EV et al.: "Synthesis, gamma-resonance spectra, and structure of laminar graphite compounds containing iron(III) chloride and molybdenum(V) chloride or iron(III) chloride and tungsten(VI) chloride", & ZH. STRUKT. KHIM. 1979, 20(5), 835-41 *
CHEMICAL ABSTRACTS, vol. 95, no. 20, 16th November 1981, page 744, abstract no. 180084y, Columbus, Ohio, US; T. DZIEMIANOWICZ et al.: "Study of the system graphite-manganese(II) chloride-aluminum chloride", & EXT. ABSTR. PROGRAM-BIENN. CONF. CARBON 1981, 15th, 379-80 *
MATERIALS SCIENCE AND ENGINEERING, vol. 31, 1977, pages 53-59, Elsevier Sequoia S.A., Lausanne, CH; E. STUMPP: "The intercalation of metal chlorides and bromides into graphite" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0311298A2 (de) * 1987-10-06 1989-04-12 Cabotex Co. Ltd. Verfahren zur Bereitung einer Einlagerungsverbindung Bereitung einer Einlagerungsverbindung
EP0311298A3 (de) * 1987-10-06 1992-01-08 Cabotex Co. Ltd. Verfahren zur Bereitung einer Einlagerungsverbindung Bereitung einer Einlagerungsverbindung
EP0578887A1 (de) * 1992-07-17 1994-01-19 Inland Steel Company Verfahren zur Herstellung von Einlagerungsverbindungen
DE102021207914A1 (de) 2020-12-15 2022-06-15 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zum Herstellen eines elektrisch leitfähigen Leiterstrangs mit zumindest einem Kohlenstoffleiter
WO2022128495A1 (de) 2020-12-15 2022-06-23 Robert Bosch Gmbh Verfahren zum herstellen eines elektrisch leitfähigen leiterstrangs mit zumindest einem kohlenstoffleiter

Also Published As

Publication number Publication date
DE3678360D1 (de) 1991-05-02
JPS6241706A (ja) 1987-02-23
US4729884A (en) 1988-03-08
EP0212940B1 (de) 1991-03-27
JPS6362446B2 (de) 1988-12-02
EP0212940A3 (en) 1988-03-16

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